Catalytic oxidation. III. The mechanism of ethylene and propylene oxidation over supported rhodium and ruthenium

Noel W. Cant*, W. Keith Hall

*Corresponding author for this work

    Research output: Contribution to journalArticlepeer-review

    38 Citations (Scopus)


    The kinetics of ethylene and propylene oxidation over Rh and Ru supported on low area α-alumina were studied and found similar to those reported earlier for the same metals supported on high area silica. The selectivities for product formation were also analogous. The most selective reaction was oxidation of C3H6 over Rh at 200 °, where substantial amounts of acrolein and acetone were formed. Substitution of deuterium for hydrogen in the olefin methyl-group reduced the rates of these reactions significantly, showing that abstraction of H from this position was involved in the rate-determining steps. The acetones formed from labeled propylenes contained deuterium in all possible positions, but exchange into the product acroleins was minor and confined mainly to the 2-position. The acrolein from CD3CHCH2 and CH3CHCD2 contained nearly equal amounts of the d1 and d2 species, but the unreacted propylene was unisomerized. The absolute values for the deuterium contents showed that the bulk of the acrolein was formed via a symmetric allyl-type intermediate, but that up to 26% of the reaction proceeded with the direct conversion of the methyl group of the olefin into the aldehyde group. The data also showed that the isotope effect for the removal of the second H (or D) from the olefin is minimal. Possible mechanisms to explain these findings are presented.

    Original languageEnglish
    Pages (from-to)310-323
    Number of pages14
    JournalJournal of Catalysis
    Issue number3
    Publication statusPublished - 1971


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